Anhydrous cosmetic makeup composition containing a fatty phase and a cosmetic treatment process using the composition

ABSTRACT

An anhydrous cosmetic makeup composition contains in addition to a fatty phase formed from oils, fatty bodies and surfactants, and optionally waxes, a vesicular lipidic phase that contains at least one ionic or nonionic amphiphilic lipid and optionally additives. The anhydrous composition also preferably contains at least one cosmetically and/or dermopharmaceutically active material.  
     In the presence of an aqueous phase these compositions release vesicles of the vesicular lipidic phase and potentialize the activity of the cosmetically and/or dermopharmaceutically active material of the composition.

[0001] The present invention relates to anhydrous cosmetic makeupcompositions comprising a fatty phase and a cosmetic treatment processusing these compositions.

[0002] Known anhydrous cosmetic compositions comprise a fatty phasecontaining mineral or organic oils, fatty bodies, surfactants intendedto provide a homogeneous phase and, most often, waxes. Dyes and pigmentsare added when it is desired that the anhydrous composition be colored.

[0003] Anhydrous cosmetic makeup compositions, such as a lip rouge, aneyelid shadow, a molded complexion foundation, and a molded cheek rouge,have as a principal purpose the application of dyes and pigments to theskin, in an even, homogeneous and durable manner.

[0004] Moreover it is known to employ cosmetic and/ordermopharmaceutical compositions which function to treat the skin ontopical application thereto.

[0005] The exigencies of modern life have necessitated efforts tosimplify cosmetic treatments by using cosmetic compositions havingseveral functions thereby reducing the number of required cosmetictreatment operations.

[0006] These efforts have involved the introduction in the anhydrousmakeup compositions of cosmetic and/or dermopharmaceutical activematerials. To this end, efforts have been made to introduce lipophilicactive materials which can be dissolved in the fatty phase of theanhydrous compositions. This fatty phase often contains a large amountof wax and its absorption by the skin or the mucous membrane is verylimited. Consequently, the effectiveness of the active materials, whichis a function of the penetration of the fatty phase in the skin, is alsoquite limited.

[0007] Consideration has also been given to introducing water-solubleactive materials. However, their introduction requires costlytechnological measures such as the lyophilization of the activematerials, then their microdispersion in the fatty phase or theincorporation of the active materials in solid supports such asmicrospheres or microcapsules and then their dispersion in the fattyphase. In this latter case, the amount of active material that can beintroduced is limited because the incorporation of solid supports,containing the active materials, modifies in a significant manner themechanical properties of the anhydrous compositions.

[0008] Thus, until now, the problem of introducing cosmetic and/ordermopharmaceutical active materials into anhydrous cosmeticcompositions has not been resolved in a satisfactory manner.

[0009] This problem also exists in the case of anhydrous cosmeticproducts such as deodorant sticks and anhydrous anti-circlecompositions. on the other hand, it is known that certain ionic ornonionic amphiphilic lipids and certain mixtures of amphiphilic lipidsare capable, on contact with an aqueous phase, of forming vesiclesconstituted by more or less spherical lamina of the vesicular lipidicphase, encapsulating an aqueous phase.

[0010] In a known manner additives can be introduced into the vesicularlipidic phase to improve the stability and the permeability of theresulting vesicles. These additives can be sterols, and in particular,cholesterol or dicetylphosphate.

[0011] In the present application and in the claims, the term“provesicular lipidic phase” designates amphiphilic lipids capable offorming vesicles, mixtures of ionic and/or nonionic amphiphilic lipidscapable of forming vesicles and amphiphilic lipids or mixtures ofamphiphilic lipids containing additives to improve the stability andpermeability of the resulting vesicles.

[0012] It is well known that these vesicles already possess, inthemselves, a cosmetic activity on topical application but especiallythat they permit the encapsulation of water-soluble and liposolublecosmetic and/or dermopharmaceutical active materials in the lipidicand/or aqueous phase. The preparation of vesicles from amphiphiliclipids and their use in cosmetics are, for example, described in Frenchapplication 2,315,991.

[0013] Moreover it is known from FR A 2,416,008, that the lipidicvesicles can be lyophilized and that after lyophilization these vesiclesretain their treating characteristics. From this one conclusion would beto introduce lyophilized liposomes and/or niosomes into anhydrouscosmetic makeup compositions. But this operation is complicated andcostly on the industrial level, for it requires producing vesicles fromamphiphilic lipids, lyophilizing them in the presence ofanti-agglomerating agents and/or cyroprotectors having no particularadvantage for cosmetic compositions, and then to incorporate them at anelevated temperature in a complex cosmetic product containing meltedoils and waxes.

[0014] According to the present invention the applicants have found thatthe provesicular lipidic phase, capable of forming vesicles in thepresence of water, retains its ability to form vesicles when it is mixedwith a fatty phase, generally employed for the production of anhydrouscosmetic compositions, which fatty phase contains organic and/or mineraloils, fatty bodies, and most often, waxes and surfactants.

[0015] In effect, as shown in the comparative examples given below, thatafter contact with water, the formation of vesicles in the aqueous phaseof satisfactory quality and significant quantity is observed. Moreover,it is noted that the resulting vesicles retain their capacity toencapsulate hydrophilic and/or lipophilic active materials and thatunder these circumstances the effectiveness of the active material,introduced into the anhydrous composition, is very clearly improved.

[0016] It was not obvious to the skilled artisan that when theprovesicular lipidic phase, capable of forming vesicles in the presenceof water, was mixed with the fatty phase, employed in the production ofanhydrous cosmetic makeup compositions, it would again be possible bymere contact with an aqueous phase, to form vesicles therein. Inparticular, it was feared that, when the provesicular lipidic phasewhich is constituted of a mixture of ionic amphiphilic lipids and/ornon-ionic amphiphilic lipids or amphiphilic lipids combined with one ormore additives, the combination of these different compounds, which canbe required for the formation of vesicles in a stable form, would bedestroyed by the oils, fatty bodies, waxes and the surfactants containedin the fatty phase of the anhydrous cosmetic product.

[0017] According to the present invention this discovery is utilized inthe production of anhydrous cosmetic compositions containing in thefatty phase, a provesicular phase capable of forming vesicles on contactwith water, these anhydrous cosmetic compositions being contacted withan aqueous phase at the time of their use to cause the formation ofvesicles.

[0018] It is necessary to note that the contact with an aqueous phase ismost often inherent in the method of application of these anhydrouscosmetic compositions.

[0019] For example, lip rouges are contacted with the labial mucousmembrane, which is rich in water, and which is regularly moistened bythe saliva; molded complexion foundations, eyelid shadows or cheekrouges are often hydrated just before application using a wet sponge;deodorant sticks are applied to the skin which is moistened by sweatsecretions.

[0020] The present invention thus-relates to an anhydrous cosmeticcomposition comprising a fatty phase which is characterized by the factthat the fatty phase contains a provesicular lipidic phase containing atleast one amphiphilic lipid capable of forming vesicles on contact withan aqueous phase.

[0021] Preferably, the cosmetic composition contains a water-solubleand/or liposoluble cosmetic and/or dermopharmaceutical active material.

[0022] The amount of the provesicular lipidic phase containing theamphiphilic lipids can represent from 0.1 to 30 percent by weight of theanhydrous composition, preferably from 1 to 20 percent.

[0023] In the provesicular lipidic phase, the amphiphilic lipidsemployed can be any amphiphilic lipid known for the production ofvesicles in the presence of water. These lipids are, in a known manner,amphiphilic lipids of natural or synthetic origin, ionic or nonionic,having, per molecule, one or more long chain, saturated or unsaturated,linear or branched hydrocarbon chains, having preferably 8 to 30 carbonatoms. These chains are, for example, oleic, lanolic, tetradecylic,hexadecylic, isostearylic, lauric or alkyl phenyl chains, and one ormore hydrophilic groups taken from hydroxyl, etheroxide, carboxyl,phosphate and amine groups.

[0024] Preferable ionic amphiphilic lipids include natural phospholipids(for example, egg lecithin or soy lecithin or sphingomyelin), syntheticphospholipids (for example, dipalmitoylphosphatidylcholine orhydrogenated lecithin). Amphoteric lipids having two lipophilic chainsor a combination of two organic ions having a long chain of oppositesigns can also be employed, as can anionic lipids.

[0025] Among the ionic amphiphilic lipids mention can be made of thosewhich are described in Luxembourg parent application 85 971, filed onJun. 23, 1985, and which are represented by the formula:

[0026] wherein

[0027] R₁ represents C₇-C₂₁ alkyl or alkenyl,

[0028] R₂ represents a C₇-C₃₁ saturated or unsaturated hydrocarbonradical, and

[0029] M represents H, Na, K, NH₄ or a substituted ammonium ion derivedfrom an amine and, principally a hydroxylated amine.

[0030] Preferable nonionic amphiphilic lipids include those containing,as hydrophilic groups, polyoxyethylenated or polyglycerolated groups, orgroups derived from esters of polyols oxyethylenated or not, or evenhydroxyamide derivatives. Advantageously, the nonionic amphiphiliclipids are selected from the group consisting of:

[0031] (1) linear or branched polyglycerol derivatives having theformula

R₃OC₃H₅(OH)O_({overscore (n)})H  (II)

[0032] wherein

[0033] —C₃H₅(OH)O— is represented by the following structures takenseparately or in admixture:

[0034] —CH₂—CHOH—CH₂O—,

[0035] {overscore (n)} has a statistical average value ranging from 1 to6,

[0036] R₃ represents:

[0037] (a) a linear or branched, saturated or unsaturated aliphaticchain containing from 12 to 30 carbon atoms; or hydrocarbon radicals oflanolin alcohols;

[0038] (b) R₄CO wherein R₄ is a linear or branched aliphatic radicalcontaining 11 to 29 carbon atoms; and

[0039] (c) R₅OC₂H₃(R₆) wherein R₅ has the meaning (a) or (b) given forR₃; —OC₂H₃(R₆)— is represented by the following structures takenseparately or in admixture:

[0040] wherein R₆ has the meaning (a) given above for R₃,

[0041] (2) polyglycerol ethers, linear or branched, having two fattychains;

[0042] (3) polyoxyethylenated fatty alcohols;

[0043] (4) polyoxyethylenated sterols and phytosterols;

[0044] (5) ethers of polyols;

[0045] (6) esters of polyols oxyethylenated or not and, in particular,esters of polyoxyethylenated sorbitol;

[0046] (7) glycolipids of natural or synthetic origin, for example thecerebrosides;

[0047] (8) polyglycerolated α-diols;

[0048] (9) hydroxyamides represented by the formula:

[0049] wherein

[0050] R₇ represents a C₇-C₂₁ alkyl or alkenyl radical,

[0051] R₈ represents a saturated or unsaturated C₇-C₃₁ hydrocarbonradical;

[0052] COA represents one of the following two groups:

[0053] (a)

[0054] wherein B is a mono or polyhydroxylated alkyl derived from aprimary or secondary amine and R₉ represents hydrogen, methyl, ethyl orhydroxyethyl, and

[0055] (b) COOZ wherein Z represents the residue of a C₃-C₇ polyol; and

[0056] (10) the ethers and esters described in French patent application90 13139 filed on Nov. 14, 1990 and having the formula

[0057] wherein

[0058] A represents —OR or

[0059] wherein R represents a saturated or unsaturated hydrocarbonradical, and

[0060] n is 2 or has a statistical average value {overscore (n)} greaterthan 1 and at most 6.

[0061] Preferably R represents a C₇-C₂₂ linear alkyl, a C₇-C₃₆ branchedalkyl, a C₁₈ alkenyl or alkylaryl having a linear or branched C₇-C₁₆alkyl chain. In the alkyl aryl radical, the aryl group is, preferably,phenyl. The alkenyl radical advantageously is an octadecene-9 yl or anoctadecanediene-9,12 yl group.

[0062] In a known manner, various additives can be combined with theamphiphilic lipids to modify their stability and permeability. In thisregard mention can be made of the optional addition of long chainalcohols and diols; sterols such as, for example, cholesterol andβ-sitosterol; long chain amines and their quaternary ammoniumderivatives; hydroxyalkylamines; polyoxyethylenated fatty amines; estersof long chain aminoalcohols, their salts and quaternary ammoniumderivatives; phosphoric esters of fatty alcohols in free or neutralizedform such as, for example, sodium dicetylphosphate and alkyl sulfatessuch as, for example, sodium cetyl sulfate; ionic derivatives ofsterols; and certain polymers such as polypeptides and proteins.

[0063] As explained above, in accordance with the invention, there canbe introduced into the fatty phase, cosmetic and/or dermopharmaceuticalactive materials. According to the present invention, only activematerials known to have a cosmetic and/or dermopharmaceutical activityon topical application and capable of being encapsulated in amphiphiliclipid vesicles can be employed.

[0064] Representative lipophilic active materials include, principally,vitamin E, esters of vitamin E, polyunsaturated fatty acids, vitamin F,sunscreen agents, antioxidants, preservatives, vitamin A, retinoic acidand its esters.

[0065] Representative water-soluble active materials include,preferably, those which permit, on admixture with the provesicularlipidic phase the production of anhydrous lamellar phases, such asglycerol, sorbitol and other polyols having a close structure. Alsouseful are amino acids such as arginine, lysine, proline and serine;vitamins such as D,L-panthenol; and sunscreen agents.

[0066] In a known manner the fatty phase comprises fatty bodies such ascocoa butter and oils. Representative oils capable of being employed inaccordance with the invention include, particularly:

[0067] mineral oils such as paraffin oil, petrolatum oil and oils havinga boiling point between 310 and 410° C.,

[0068] oils of animal origin, such as perhydrosqualene,

[0069] vegetable oils such as sweet almond oil, calophyllum oil, palmoil, avocado oil, jojoba oil, olive oil, ricin oil and cereal germ oils,such as wheat germ oil,

[0070] silicone oils such as dimethylpolysiloxane,

[0071] synthetic esters such as purcellin oil, butyl myristate,isopropyl myristate, cetyl myristate, isopropyl palmitate, butylstearate, hexadecyl stearate, isopropyl stearate, octyl stearate,isocetyl stearate, decyl oleate, hexyl laurate, propylene glycoldicaprylate and di-isopropyl adipate,

[0072] organic alcohols such as oleic alcohol, linoleic alcohol,lanolenic alcohol, isostearyl alcohol and octyl dodecanol, and

[0073] esters derived from lanolic acid such as isopropyl lanolate andisocetyl lanolate.

[0074] Other oils that can also be employed include acetyl glycerides,the octanoates and decanoates of alcohols and polyalcohols, such asthose of glycol and glycerol, ricinoleates of alcohols and polyalcoholssuch as those of cetyl.

[0075] Most often waxes are also employed and representative waxes,employed in the present invention, include:

[0076] mineral waxes such as microcrystalline waxes, paraffin waxes andpetrolatum waxes,

[0077] fossil waxes such as ozokerite, montan wax,

[0078] waxes of animal origin such as beeswax, spermaceti, lanolin wax,derivatives of lanolin such as lanolin alcohols, hydrogenated lanolin,hydroxylated lanolin, acetylated lanolin, lanolin fatty acids, andacetylated lanolin alcohol,

[0079] waxes of vegetable origin such as candelilla wax, Carnauba wax,and Japan wax,

[0080] hydrogenated oils, solid at 25° C., such as hydrogenated ricinoil, hydrogenated palm oil, hydrogenated tallow and hydrogenated cocoaoil,

[0081] fatty esters, solid at 25° C., such as propylene glycolmonomyristate and myristyl myristate.

[0082] Among other waxes, mention can be made of cetyl alcohol, stearylalcohol, mono-, di- and triglycerides solid at 25° C., stearicmonoethanol amide, colophane and its derivatives such as glycol andglycerol abietates, sucroglycerides and the oleates, myristates,lanolates, stearates and dihydroxystearates of calcium, magnesium, zincand aluminum.

[0083] Pigments are introduced when the cosmetic composition must becolored.

[0084] Generally there are also added surfactant agents such assuccinylglycerides, alkylphosphates, esters of fatty acids such aspolysorbates sold under the trade name “TWEEN” by ICI Americas andesters of polyethyleneglycol such as those sold under the name “BRIJ”,by ICI.

[0085] The anhydrous cosmetic composition, according to the invention,is prepared by mixing the various components. Preferably, the materialsconstituting the fatty phase and the materials constituting theprovesicular lipidic phase are mixed separately. Then the resulting twophases are mixed until a homogeneous preparation is obtained. In thislatter case the cosmetic and/or dermopharmaceutical active materials arepreferably introduced into the-provesicular lipidic phase.

[0086] The present invention also relates to a process for the cosmetictreatment of the skin characterized by the fact that the anhydrouscosmetic composition, described above, is applied to the skin, thecosmetic composition being in contact with an aqueous phase when it isapplied to the skin.

[0087] According to the invention, the contact of the anhydrous cosmeticcomposition with an aqueous phase can be effected just beforeapplication of the composition onto the skin. In this situation thecomposition can be removed with a wet sponge and the composition isspread on the skin using this sponge.

[0088] Contact can also be effected by spreading the composition on skinpreviously moistened either with saliva or perspiration, or by the watercontained in the mucous membranes, or using an aqueous phase derivedfrom an external source.

[0089] Contact can also be effected after application of the anhydrouscosmetic substance. In this case also, the aqueous phase can beconstituted by perspiration or saliva or provided from an externalsource.

[0090] The objectives, characteristics an advantages of the presentinvention will appear more clearly from the examples given below as anillustration and without any limitation.

EXAMPLE 1 (Comparison)

[0091] (1) Preparation of a Fatty Phase A Having the FollowingComposition Polybutene  5.04 g Lanolin oil 20.38 g Octoxy glycerylbehenate 20.38 g Stearyl heptanoate  9.84 g Jojoba oil  9.84 g Ricin oil19.20 g Butylhydroxytoluene  0.06 g Butylhydroxyanisole  0.06 gMicrocrystalline wax  7.60 g Polyethylene 500 70.60 g

[0092] The mixture of the various compounds above is effected at atemperature between 100 and 120° C. with stirring, using a bar magnet,until a well homogenized preparation is produced.

[0093] (2) Starting with this Fatty Phase A the Following VariousCompositions are Prepared:

[0094] Composition A1: (not containing a provesicular lipidic phase butcontaining a liposoluble active material)

[0095] 1% of α-tocopherol acetate, which is a liposoluble activematerial is mixed with 99% of the fatty phase A defined above.

[0096] Composition A2: (containing a nonionic provesicular lipidic phasebut no liposoluble active material)

[0097] (a) A provesicular lipidic phase having the followingcompositiion is prepared by comelting at 100° C. under nitrogen: anonionic amphiphilic lipid having the formula

C₁₆H₃₃OC₃H₅(OH)O_({overscore (n)})H  (V)

[0098] wherein

[0099] —C₃H₅(OH)O— is represented by the following structures, taken inadmixture or separately:

{overscore (n)} has a statistical average value 4.75 g equal to 3cholesterol 4.75 g dicetyl phosphate 0.5 g

[0100] (b) composition A2 is prepared by mixing 90% of fatty phase A and10% of the above-described provesicular lipidic phase.

[0101] Composition A3: (containing a nonionic provesicular lipidic phaseand containing a liposoluble active material)

[0102] (a) A provesicular lipidic phase having the following compositionis prepared by comelting at 100° C. under nitrogen: nonionic amphiphiliclipid having 4.75 g formula V cholesterol 4.75 g dicetyl phosphate 0.5 gα-tocopherol acetate 1 g

[0103] (b) Composition A3 is prepared by mixing 89% of the above fattyphase A with 11% of the above-described provesicular lipidic phase.Composition A3 then contains 1% of α-tocopherol acetate.

[0104] Composition A4: (containing an ionic provesicular lipidic phaseand not containing a liposoluble active material)

[0105] Employing the same process as that used for producing compositionA3, a composition A4 is prepared and comprises:

[0106] 90 weight percent of fatty phase A

[0107] 10 percent of a vesicular lipidic phase constituted of 6% of soylecithin sold under the trade name “LECINOL S 10” by Nikko, and 4% ofphytosterol oxyethylenated with 5 moles of ethylene oxide, sold underthe trade name “GENEROL 122 E5” by Henkel.

[0108] Composition A5: (containing an ionic provesicular lipidic phaseand a liposoluble active material)

[0109] Using the same process as that employed in producing compositionA1, composition A5 is prepared and consists of

[0110] 89% of fatty phase A and

[0111] 11% of a provesicular lipidic phase consisting of 6% of “LECINOLS10”, 4% of phytosterol oxyethylenated with 5 moles of ethylene oxidesold under the trade name “GENEROL 122 E5” by Henkel and 1% ofα-tocopherol acetate.

[0112] (3) Comparative Tests

[0113] A 1 g film of each of compositions A, A1, A2, A3, A4 and A5 isdeposited in a Petri dish and then covered with 10 g of water.

[0114] The dish is hermetically sealed, then stirred in a shakingmachine for 24 hours at ambient temperature.

[0115] After 24 hours, the aqueous phase is recovered and weighed. Afirst aliquot portion of this resulting aqueous phase is recovered andobserved with a phase contrast microscope. A second aliquot portion ofthis aqueous phase is lyophilized and then taken up in a solvent(chloroform). The dosage of the vesicular lipids (V) and cholesterol orphytosterol is effected by high performance thin layer chromatography(HPTLC) after carbonization, the reading of the plates being made on aShimadzu densitometer. The dosage of the α-tocopherol acetate is made byhigh pressure liquid chromatography (HPLC).

[0116] The results are given in Table I, below. TABLE 1 Weight ratioAmount of (V)/chole- Amount cholesterol sterol or of α- Result of Compo-Amount of or phytost- tocopherol microscope sition lipid (V)phytosterol* erol (%) in % examination  A** 0    0    — 0 no vesicles A1* 0    0    — 0 no vesicles A2 5% 5% 50/50 0 numerous vesicles A3 6%6% 50/50 1.5 numerous vesicles A4 8% 8% 60/40 0 vesicles A5 8% 6% 60/403 vesicles

[0117] The results given above show that when the fatty phase of ananhydrous cosmetic composition is added to a provesicular lipidic phase,it is possible, on contact with an aqueous phase, to release, in thisaqueous phase, vesicles having the same composition as the provesicularlipidic phase added and that, if there is introduced into thecomposition a liposoluble active material, the latter is also releasedin the aqueous phase with the vesicles formed. The mere mixing of theliposoluble active material with the fatty phase does not release theα-tocopherol in the aqueous phase.

[0118] The chromatography dosage techniques employed in this example areas follows:

[0119] HPTLC dosage technique.

[0120] On a 60 Merck silica gel plate without fluorescence indicator, 20μl of the sample or standard are deposited. The standardization range iseffected from 0.5 mg/ml to 3 mg/ml. Migration is made in a vertical tankwith an 80/20 chloroform/methanol mixture. Detection is made bypulverization with HSO at 20% in water, then carbonization at 170° C.for 5 minutes. The reading is made on a Shimadzu densitometer at:

[0121] 400 nm for cholesterol,

[0122] 470 nm for the nonionic amphiphilic lipid of formula (V) and theoxyethylenated phytosterol (GENEROL 122 E5), and

[0123] 530 nm for hydrogenated lecithin, sold under the trade name“LECINOL S10” by Nikko.

[0124] HPLC dosage technique of α-tocopherol acetate. Column type RP 18(5 μm) Lichrosorb quality sold by Merck Eluant pure methanol Flow rate 1.5 ml/mm λ 280 nm Injection  10 μl

[0125] The standards and samples are in solution in chloroform.

EXAMPLE 2 (COMPARISON)

[0126] Composition prepared starting with a lip rouge fatty phase

[0127] (1) Preparation of the Compositions

[0128] As in Example 1 a base B is prepared having the followingcomposition: Polybutylene  5.04 g Lanolin oil 20.38 g Octoxy glycerylbehenate 20.38 g stearylheptanoate  9.84 g Jojoba oil  9.84 g Ricin oil19.20 g Butylhydroxytoluene  0.06 g Butylhydroxyanisole  0.06 g

[0129] and to which are added, so as to obtain fatty phases, variousamounts, set forth in Table II below, of polyethylene wax, sold underthe trade name “POLYWAX 500” by Bareco, and microcrystalline wax.

[0130] To the resulting fatty phases two provesicular lipidic phases areadded.

[0131] Provesicular lipidic phase (1) has the following composition:nonionic lipid of formula (V) 47.5 g described in Example 1 cholesterol47.5 g dicetylphosphate  5.0 g

[0132] Provesicular lipidic phase (2) has the following composition:“LECINOL S10” 60.0 g cholesterol 30.0 g palmitoylcollagenic acid, sold10.0 g by Rhone-Poulenc under the trade name “LIPACIDE PCO”

[0133] The two provesicular lipidic phases are prepared by comelting thecomponents at 100° C. under nitrogen.

[0134] Optionally glycerine, which is a water-soluble active material,is added by premixture with the provesicular phase.

[0135] Compositions B1 to B9 are thus obtained, the compositions ofwhich are given in Table II below: TABLE II Mixture wt for wt Mixture wtfor wt of glycerine and of glycerine and provesicular provesicularMicrocrystalline Polyethylene wax lipidic phase (1) lipidic phase (2)Compositions Base B in g wax in g in g Glycerine in g in g in g  B1*78.0 8.50 8.50  5.0 0 0  B2* 72.8 8.60 8.60 10.0 0 0  B3* 67.7 8.65 8.6515.0 0 0 B4 73.8 8.10 8.10 10.0 0 B5 65.5 7.25 7.25 20.0 0 B6 54.8 7.607.60 30.0 0 B7 73.8 8.10 8.10 0 10.0 B8 65.5 7.25 7.25 0 20.0 B9 54.87.60 7.60 0 30.0

[0136] (2) Comparative Tests

[0137] A 1 g film of each of fatty phases B1 to B9 is deposited in aPetri dish, then covered with 10 g of water. The dish is hermeticallysealed and then agitated on a shaker machine for 24 hours at ambienttemperature. After 24 hours the aqueous phase is recovered and weighed.

[0138] Dosage of the glycerine is effected enzymatically using the KitSigma 337 A.

[0139] The results are given in Table III, below TABLE III Amount ofglycerine dosed in the aqueous phase, in % of the Composition initialamount Potentialization (1)  B1*  8  B2* 10  B3*  7 B4 43 B4/B1: X5.4 B559 B5/B2: X5.9 B6 86  B6/B3: X12.3 B7 20 B7/B1: X2.5 B8 31 B8/B2: X3.1B9 42 B9/B3: X6  

[0140] The results achieved in this example show that the inventionpotentializes the release of the glycerine in an aqueous environment,whatever the nature of the provesicular lipidic phase employed and theglycerine concentration in this phase.

[0141] The dosage of the glycerine according to the Sigma protocol ofthe Kit No. 337 is effected using the reagent defined below according tothe reactions:

[0142] Glycerol+ATP GK_(>)G-I-P+ADD

[0143] G-I-P+O₂ GPO_(>)DAP+H₂O₂

[0144] H₂O₂+4AAP+ESPA PDA_(>)colored quinoneimine+H₂O

[0145] ATP—Adenosine Triphosphate

[0146] GK—Glycerol Kinase

[0147] GIP—Glycerol 1 phosphate

[0148] ADP—Adenosine 5′-diphosphate

[0149] GPO—Glycerol phosphate oxydase

[0150] DAP—Dihydroxyacetone phosphate

[0151] 4-AAP—4 aminoantipyrine

[0152] ESPA—Sodium N-ethyl-N (3-sulfopropyl) m-anisidine

[0153] POD—Peroxydase

[0154] The reading is made at 540 nm.

[0155] The reagent employed has the following composition: ATP 0.375mmol/l Magnesium salt 3.75 mmol/l Sodium N-ethyl-N-(3-sulfopropyl) 2.11mmol/l m-anisidine Glycerol kinase 1.250 U/l Glycerol phosphate oxydase2500 U/l Peroxydase 2500 U/l Buffer pH 7

[0156] As a comparison, the dosage of a blank and various samples iseffected in the following proportions: Blank Sample Reagent 3 ml 3 mlSample — 0.01 ml Water 0.01 ml —

[0157] The calculation of the concentration is made relative to theoptical density of a known standard.

EXAMPLE 3 (COMPARISON)

[0158] Complexion Foundation Released From Ionic Liposomes Charged withGlycerine or Sorbitol

[0159] (1) Preparation

[0160] The fatty phase C having the composition given below is producedby mixing waxes and oils at 80° C. with stirring until a homogeneousmixture is obtained. The pigments and fillers are added always at 80° C.and with stirring until a homogeneous color is obtained. The remainderof the components are added and the temperature is maintained at 80° C.for 2 hours with stirring.

[0161] The resulting fatty phase C has the following composition:Microcrystalline wax 4 g Carnauba wax 6 g Octyl palmitate 14 gHydrogenated polyisobutane 17.6 g Trilaurin 7 g Propyl paraben 0.1 gIron oxide (yellow) 4.9 g Iron oxide (brown-yellow) 1.9 g Titaniumdioxide 16.5 g Iron oxide (black) 0.7 g Zinc oxide 3.0 g Benzophenone-30.5 g Octyl methoxycinnamate 0.5 g Dimethicone, sold under the tradename 0.3 g “SILBIONE 70047 V300” by Rhone Poulenc Nylon, sold under thetrade name 8.0 g “L'ORGASOL 2002 Natural EXTRA COS” by Ato Mica 15.0 g

[0162] Starting with this fatty phase C, the below compositions areproduced, on mixture, in various amounts, of glycerine or sorbitol witha provesicular lipidic phase consisting of a mixture of “LECINOL S10”and an oxyethylenated phytosterol (GENEROL 122 ES), in a 60/40 weightproportion, at a temperature of 80° C. with stirring for 1 hour. LECINOLS10/ Fatty phase Glycerine Sorbitol phytosterol Composition C in G in gin g 60/40 in g C1 100 — — — C2 95 5 — — C3 95 — — 5 C4 90 5 — 5 C5 95 —5 — C6 90 — 5 5

[0163] (2) Tests

[0164] These compositions were tested in accordance with the methodemployed in Example 1:

[0165] Operating Procedure:

[0166] A 1 g film of each of the bases C1 to C6 is deposited in a Petridish and then covered with 10 g of water.

[0167] The dish is hermetically sealed and then stirred on a shakermachine for 24 hours at ambient temperature. After 24 hours, the aqueousphase is recovered and quantified. Dosage of the lipids is made byHPTLC, the glycerine is dosed enzymatically as described above, and thesorbitol is dosed enzymatically in accordance with the following method.

[0168] Dosage Method of the Sorbitol

[0169] The method is based on the following reaction:D-sorbitol+NAD^(SDH>)Fructose+NADH, H+(SDH=sorbitol dehydrogenase;NAD=nicotinamide dehydrogenase).

[0170] Under the test conditions, the reaction is completely displacedto the right. The amount of NADH, H+ formed in the reaction isstoichiometric with the amount of sorbitol; it is determined bymeasuring the absorbance increase at 340 nm.

[0171] Reagents—Preparation of the Solutions

[0172] Solution 1: pyrophosphate 0.2 M, pH=9.5

[0173] Dissolve 8.92 g of Na₄P₂O₇.10H₂O in 80 ml of distilled water.Adjust to pH 9.5 with 1N HCl then to a volume of 100 ml with distilledwater.

[0174] Solution 2: Dissolve 40 mg of NAD in 2 ml of distilled water.

[0175] Solution 3: Sorbitol dehydrogenase (SDH)

[0176] Dissolve 2 mg in 500 μl of distilled water.

[0177] Operating Method

[0178] The following solutions are prepared: Blank Sample Solution 11.00 ml 1.00 ml Solution 2 0.10 ml 0.10 ml Sample — 0.20 ml Distilledwater 1.70 ml 1.50 ml

[0179] The reaction is started by adding in each tank 0.05 ml ofsolution 3. The contents are mixed and the optical densities are readafter 60 minutes against distilled water at 0.412 λ Abs., −λ Abs. beingthe absorbance of the sample less the absorbance of the blank.

[0180] The results obtained with the complexion foundation compositionstested are as follows: TABLE IV Weight ratio Amount of active Formu-Amount of LECINOL material in the Potentia- lation lipids**S10/phytosterol aqueous phase** lization C1* — — — — C2* — — 12 — C3* 760/40 — — C4 6 60/40 78 C4/C2: X6.5 C5* —  8 — C6 6 60/40 49 C6/C5: X6.1

[0181] The above results show that in the presence of a provesicularlipidic phase, vesicles having the same composition as the lipidic phaseare released by mere contact with an aqueous environment. On the otherhand, it is shown that the formed vesicles potentialize the release ofwater-soluble active materials.

EXAMPLE 4

[0182] Preparation of a “Two Way Cake”

[0183] A binder L having the following composition is prepared:Petrolatum oil 56.5 g Ricin oil 10.8 g Petrolatum 10.0 g Isopropylmyristate 7.2 g Oleic alcohol 10.0 g Lanolin 5.5 g

[0184] There is also prepared, by comelting at 100° C. under nitrogen, aprovesicular lipidic phase (3) having the following composition:Nonionic amphiphilic lipid of 47.5 g formula (V) of Example 1Cholesterol 47.5 g Dicetyl phosphate 5.0 g

[0185] The fillers, pigments and powders are then added until ahomogeneous mixture is obtained. The binder and the provesicular lipidicphase previously heated to bring them to the liquid state are added. Thewhole is then ground together in order to obtain a homogenouscomposition.

[0186] The “two way cake” obtained has the follows composition: Talc,sufficient amount for 100.0 g Mica 20.0 g Titanium oxide 5.0 g Zincstearate 2.0 g Nylon powder 5.0 g Iron oxide 2.0 g Octyl dimethylparaaminobenzoate 0.5 g Perfume 0.2 g Preservative 1.0 g Binder L 8.0 qProvesicular lipidic phase (3) 2.0 g Glycerine 2.0 g Vitamin E 0.1 g

[0187] This composition is applied to the face by the user with a wetsponge.

We claim:
 1. A cosmetic treatment process comprising applying to theskin or labial mucous membrane an anhydrous cosmetic makeup compositioncomprising a fatty phase, said anhydrous cosmetic composition beingprepared by mixing said fatty phase with a provesicular lipidic phasecontaining at least one amphiphilic lipid capable of forming vesicles oncontact with an aqueous phase and said cosmetic composition being incontact with an aqueous phase when it is applied.
 2. The process ofclaim 1 wherein said composition is applied to previously wetted skin orlabial mucous membrane.
 3. The process of claim 1 wherein saidcomposition is contacted with an aqueous phase after application.
 4. Theprocess of claim 1 which includes introducing into said cosmeticcomposition at least one water-soluble cosmetic and/ordermopharmaceutical active material and/or at least one liposolublecosmetic and/or dermopharmaceutical active material.
 5. The process ofclaim 1 wherein said provesicular lipidic phase is mixed with said fattyphase in an amount such that the provesicular lipidic phase representsfrom 0.1 to 30 weight percent of said anhydrous makeup cosmeticcomposition.
 6. The process of claim 5 wherein the provesicular lipidicphase is mixed with the fatty phase in an amount such that theprovesicular lipidic phase represents from 1 to 20 weight percent of thecosmetic composition.
 7. The process of claim 1 wherein saidprovesicular lipidic phase contains at least one ionic amphiphiliclipid.
 8. The process of claim 7 wherein said ionic amphiphilic lipid isa natural or synthetic phospholipid.
 9. The process of claim 7 whereinsaid ionic amphiphilic lipid has the formula

wherein R₁ represents a C₇-C₂₁ alkyl or alkenyl radical, R₂ represents asaturated or unsaturated C₇-C₃₁ hydrocarbon radical, and M represents H,Na, K, NH₄ or an ammonium ion derived from an amine.
 10. The process ofclaim 9 wherein M is a hydroxylated amine.
 11. The process of claim 1wherein said provesicular lipidic phase contains at least one nonionicamphiphilic lipid selected from the group consisting of (1) a linear orbranched polyglycerol derivative having the formulaR₃OC₃H₅(OH)O_({overscore (n)})H  (II) wherein —C₃H₅(OH)O— representsthe following structures taken in admixture or separately:—CH₂—CHOH—CH₂O—,

{overscore (n)}has a statistical average value ranging from 1 to 6, R₃represents: (a) a linear or branched, saturated or unsaturated aliphaticchain containing from 12 to 30 carbon atoms, or a hydrocarbon radical ofa lanolin alcohol, (b) R₄CO wherein R₄ is a linear or branched C₁₁-C₂₉aliphatic radical, (c) R₅OC₂H₃(R₆) wherein R₅ has the meaning (a) or(b) above for R₃; —OC₂H₃(R₆)— represents the following structures takenin admixture or separately:

wherein R₆ has the meaning (a) for R₃, (2) a linear or branchedpolyglycerol ether having two fatty chains; (3) a polyoxyethylenatedfatty alcohol; (4) a polyoxyethylenated sterol or phytosterol; (5) apolyol ether; (6) a polyol ester oxyethylenated or not; (7) a natural orsynthetic glycolipid; (8) a polyglycerolated α-diol; (9) a hydroxyamidehaving the formula

wherein R₇ represents a C₇-C₂₁ alkyl or alkenyl radical, R₈ represents asaturated or unsaturated C₇-C₃₁ hydrocarbon radical, and —COA representsa member selected from the group consisting of

wherein B is an alkyl radical derived from a primary or secondary, monoor poly hydroxylated amine and R₉ represents hydrogen, methyl, ethyl orhydroxyethyl, and (ii) COOZ wherein Z represents the residue of a C₃-C₇polyol, and (10) an ether or ester having the formula

wherein A represents —OR or

wherein R represents a saturated or unsaturated hydrocarbon radical andn has a value equal to 2 or a statistical average value {overscore (n)}greater than 1 and at most equal to
 6. 12. The process of claim 1wherein said provesicular lipidic phase contains at least one ionicamphiphilic lipid and at least one nonionic amphiphilic lipid.
 13. Theprocess of claim 1 wherein said provesicular lipidic phase contains atleast one additive to improve the stability and permeability ofvesicles.
 14. The process of claim 13 wherein said additive is selectedfrom the group consisting of a long chain alcohol or diol; a quaternaryammonium compound; a hydroxyalkylamine; a polyoxyethylenated fattyamine; a long chain aminoalcohol ester or a salt thereof or a quaternaryammonium derivative thereof; a phosphoric ester of a fatty alcohol infree or neutralized form; an alkyl sulfate; and ionic derivative of asterol or polymer.
 15. The process of claim 5 wherein said liposolublecosmetic and/or dermopharmaceutical active material is selected from thegroup consisting of vitamin E, an ester of vitamin E, a polyunsaturatedfatty acid, vitamin F, a sunscreen agent, an antioxidant, apreservative, vitamin A, retinoic acid and an ester of retinoic acid.16. The process of claim 5 wherein said water-soluble cosmetic and/ordermopharmaceutical active material is selected from the groupconsisting of glycerol, sorbitol, an amino acid, a sunscreen agent and avitamin.
 17. An anhydrous cosmetic makeup composition comprising amixture of a fatty phase and a provesicular lipidic phase containing atleast one amphiphilic lipid capable of forming vesicles on contact withan aqueous phase.
 18. The composition of claim 17 which also contains atleast one water-soluble cosmetic and/or dermopharmaceutical activematerial and/or at least one liposoluble cosmetic and/ordermopharmaceutical active material.
 19. The composition of claim 17wherein said provesicular lipidic phase is present in an amount rangingfrom 0.1 to 30 percent by weight of said composition.
 20. Thecomposition of claim 17 wherein said provesicular lipidic phase ispresent in an amount ranging from 1 to 20 percent by weight of saidcomposition.
 21. The composition of claim 17 wherein said provesicularlipidic phase contains at least one ionic amphiphilic lipid.
 22. Thecomposition of claim 21 wherein said ionic amphiphilic lipid is anatural or synthetic phospholipid.
 23. The composition of claim 21wherein said ionic amphiphilic lipid has the formula

wherein R₁ represents a C₇-C₂₁ alkyl or alkenyl radical, R₂ represents asaturated or unsaturated C₇-C₃₁ hydrocarbon radical and M represents H,Na, K, NH₄ or an ammonium ion derived from an amine.
 24. The compositionof claim 23 wherein M is an ammonium ion derived from hydroxylatedamine.
 25. The composition of claim 17 wherein said provesicular lipidicphase contains at least one nonionic amphiphillic selected from thegroup consisting of: (1) a linear or branched polyglycerolatedderivative having the formula R₃OC₃H₅(OH)O_({overscore (n)})H  (II)wherein —C₃H₅(OH)O— represents the following structures taken inadmixture or separately: —CH₂—CHOH—CH₂O—,

{overscore (n)} has a statistical average value ranging from 1 to 6, R₃represents: (a) a linear or branched, saturated or unsaturated aliphaticchain containing from 12 to 30 carbon atoms, or a hydrocarbon radical ofa lanolin alcohol, (b) R₄CO wherein R₄ is a linear or branched C₁₁-C₂₉aliphatic radical, or (c) R₅OC₂H₃(R₆) wherein R₅ has the meaning (a)or (b) of R₃; —OC₂H₃(R₆)— represents the following structures taken inadmixture or separately:

wherein R₆ has the meaning (a) for R₃; (2) a linear or branchedpolyglycerol ether having two fatty chains; (3) a polyoxyethylenatedfatty alcohol; (4) a polyoxyethylenated sterol or phytosterol; (5) apolyol ether; (6) a polyol ester oxyethylenated or not; (7) a natural orsynthetic glycolipid; (8) a polyglycerolated a-diol; (9) a hydroxyamidehaving the formula

wherein R₇ represents a C₇-C₂₁ alkyl or alkenyl radical, R₈ represents asaturated or unsaturated C₇-C₃₁ hydrocarbon radical, —COA represents

wherein B is an alkyl radical derived from a primary or secondary, monoor polyhydroxylated amine, and R₉ represents hydrogen, methyl, ethyl orhydroxyethyl, or (ii) —COOZ wherein Z represents the residue of a C₃-C₇polyol, and (10) an ether or ester having the formula

wherein A represents —OR or

wherein R represents a saturated or unsaturated hydrocarbon radical andn has a value of 2 or is a statistical average value n greater than 1and at most equal to
 6. 26. The composition of claim 17 wherein saidprovesicular lipidic phase contains at least one ionic amphiphilic lipidand at least one nonionic amphiphilic lipid.
 27. The composition ofclaim 17 wherein said provesicular lipidic phase contains at least oneadditive to improve the stability and permeability of vesicles.
 28. Thecomposition of claim 27 wherein said additive is selected from the groupconsisting of a long chain alcohol or diol; a quaternary ammoniumcompound; a hydroxyalkylamine; a polyoxyethylenated fatty amine; a longchain aminoalcohol ester or a salt thereof or a quaternary ammoniumderivative thereof; a phosphoric ester of a fatty alcohol in free orneutralized form; an alkyl sulfate and an ionic derivative of a sterolor polymer.
 29. The composition of claim 18 wherein said liposolublecosmetic and/or dermopharmaceutical active material is selected from thegroup consisting of vitamin E, a vitamin E ester, a polyunsaturatedfatty acid, vitamin F, a sunscreen agent, an antioxidant, apreservative, vitamin A, retinoic acid and an ester of retinoic acid.30. The composition of claim 18 wherein said water-soluble cosmeticand/or dermopharmaceutical active material is selected from the groupconsisting of glycerol, sorbitol, an amino acid, a sunscreen agent and avitamin.